Manufacture of vat dyestuffs



Patented June 4, 1929.

UNETED STATES PATENT OFFICE.

MAXIMILIAN P. SCHMIDT AND WILHE'LM NEUGEBAUER, 0F BIEBRICH-ON-THE- RHINE, GERMANY, ASSIGNORS, BY MESNE ASSIGNMENTS, T0 GRASSELLI DYE- ST'UFF CORPORATION, OF NEW YORK, H. Y., A CORPORATION OF DELAWARE; I

MANUFACTURE OF VAT DYESTUFFS.

No Drawing. Application filed December 17, 1923, Serial No. 681,273, and in Germany December 2?, 1922.

The present invention relates to new vat dycstufi s containing a perylene nucleus and to a process for preparing the same.

Vile have found that new highly valuable vat dyestufis are obtained by causing a compound of the general formula:

The reaction probably proceeds in such a manner that the negative substituent of the perylene nucleus reacts with the hydrogen atom of the OH, SH and NH roup of the hydrocarbon.

As is more fully stated in the examples aliphatic as well as aromatic hydrocarbons are operative, provided they are substituted by a substituent of the above mentioned Preferably we carry out our process in the presence of a small amount of an acid binding substance such as potassium hydroxide.

The compounds of the above given formula to be used as starting materials are obtainable in several 'Ways. For instance, compounds being substituted by at least one nitro group are described in the German patent specification No. 276,358 and compounds-being substituted by halogen in the German patent specification No. 280,830. Other derivatives may be produced, for instance, by treating the diimides of perylenetetracar- I during about 8 hours with 20 parts of phenol and 3 parts of potassium hydroxide. The mass is then treated with a diluted soda-lye, filtered and washed. The remaining coloring matter forms a blue vat and dyes cotton violet-blue. The dyestuit contains only a very small quantity of chlorine. The fastness to chlorine is very good.'

Era-mph ll.3 parts of the brominated dyestufiF, obtainable by bromination of the diiinide of perylenetetracorboxylic acid under pressure, are heated during about 12 hours in the oil-bath to 200-210 centigrade with a mixture of phenolate and phenol prepared from 2,5 parts of metallic sodium and parts of phenol. The mass is treated with a diluted soda-lye, filtered, washed and dried. Thedyestufl forms a blue-violet vat and dyes cotton a little redder than the coloring matter obtained according to Example I. The fastness to chlorine is good.

Example I I I .3 parts of the diimide of dichloropery]enetetracarboxylic acid (cfr. EX- ample I) are boiled with 30 parts of p-toluidine and 4 parts of calcinated sodium-carbonate during about 15 hours. The mass is introduced into diluted hydrochloric acid, filtered and washed until neutral reaction takes place. The dyestulf dyes cotton from the violet-blue vat a bordcaux of a very good fastness.

Example I V.1,5 parts of the diimide of dichloroperylenetetracarboxylic acid are heated to boiling point with 30 parts of alcohol of 95% and 3 parts of potassium hydroxide during about 12 hours. The mass is diluted with water, filtered and washed with water. The coloring matter dyes cotton in bordeaux shades of a good fastness.

Ea'mnple V.3 parts of the. dyestuff obtainable by chlorination of the diphenyl diimide of perylenetetracarboxylic acid are boiled during about 6 hours with 50 parts of phenol and 5 parts of potassium hydroxchlorosulfonic acid, or fuming sulphuric acid, the anhydride of perylenctetracerboxylic acid and condensing the totruchloro-compmand with o-phenylene-diamine advantageously in glacial acetic acidyand having the following probable constitution are heated to the boilin oint and hept there for about 9-10 hours wit 1 about l0, parts of phenol and about 10 parts of potassium hydroxide in a vessel titted with devices for cooling and stirring.

The reaction-product may be isolated by treating the melt with diluted soda-lye for the purpose of dissolving the phenol, whereupon the mass is filtered washed and dried. The dyestufl' is a bluish-black powder soluble in concentrated sulfuric acid with a blue color, forming a greenish-blue hydrosulfite vat, "from which cotton is dyed in fast blue tints. The initial coloring matter dyes a blueviolet.

Ewamplc VI I .-3 parts of the nitro-color ing matter obtainable by nitrating for a short time perylene-tetracarbox lic acid diimide with concentrated nitric acid according to the process described in Example 1 of the German patent specification 276,358 (diiinide of, the nitroperylenetetracarboxylic acid) are heated with a mixture of phenolate and.

phenol prepared from 3 parts of metallic sodium and parts of phenol to about 200-210 C. during about 8 hours in the oilbath. The reaction-product is isolated by introducing it into diluted soda-lye, filtrating; washing and drying. The dyestufi ohtained dyes cotton violet shades of a good tastness to chlorine.

We claim: 1. The process which comprises cohdensing a compound of the general formula:

) wherein X represents hydrogen but at least one X represents a negative substituent and lit represents hydrogen, alkyl or phenyl, with g wherein X represents hydrogen but at least one X represents halogen and R represents hydrogen, elk l or phenyl to be acted upon by a hydrocarbon being substituted Iii y a substituent of the group including -0 --SltI M i a- I v I 3. The process which comprises causing a compound of the general formula:

wherein X represents hydrogen but at least one X. reprets chlorine end R stands for hydrogen, alkyl or phenyl, to he acted upon 4. The process which comprises condensing 5 by a hydrocarbon being substituted by a with a phenol a compound of the general forsubstituent of the group including OH, mula:

wherein X representshydrogen but at least 5.. The process which comprises condens one X represents a negative substituent and R ing with a phenol a compound of the general 10 stands for hydrogen, alkyl or phenyl. formula:

V x x wherein X represents hydrogen but at least 6. The process which comprises condens- 15 one X represents halogen and R standsfor ing with a, phenol a compound of the genhydrogen, alkyl or phenyl. eral' formula:

wherein X represents hydrogen but at least phenyl and X stands for hydrogen but at one. X represents chlorine and It stands for least one X represents the phenoxy group.

hydrogen, alkyl or phenvl.

7. As new products the vet dyestulls of inp; obtainable by condensing the diiniide of the general formula:

ifts) wherein R represents hydrogen, alkyl or phenyl and X represents hydrogen but at least one X represents a lnonovnlent suhstitw ent ol' the group: UR, SR1: Nlllt in which It stands for a hydroenrlmn residue, said wherein R'represents hydrogen, itlkyl or aryl. dyestull's being dm-k-hrown to black powders forming new vets from which the liber is dyed red to blue tints.

&,;As new products the vet dyestuffs of the general formula:

wherein R represents hydrogen, alkyl or 9. As a new product the vet dyestutl' hethe diehloro perylene enrlmxylie acid with )henol forming :1 blue vnt from which cotton is dyed violet-blue tints. I

10. As new products the vat dyestutfs of the following formula 11. As new products the vet dyestuffs of the following constitution:

iln testimony whereof we have signed our names to this specification.

' MAXEMILIAN P. SCHMIDT.

i/VKLHELM NEUGE l tA U ER. 

